Esters of acrylic and methacrylic acids with polyamino alcohols

ABSTRACT

A SERIES OF ESTERS OF ACRYLIC AND METHACRYLIC ACID CONTAINING IN THEIR ALCOHOL RESIDUE TWO OR THREE TERT-ALKYLAMINO OR TERT-AMINO GROUPS OF VARIOUS STRUCTURES. THERE ARE DISCLOSED DIFFERENT METHODS FOR THEIR PRODUCTION: BY THE REACTION OF DI- OR TRIAMINOALKANOLS WITH ACRYLIC OR METHACRYLIC ACIDS, THEIR CHLORIDES OR LOWER ALKYL ESTERS.

United States Patent Office,

3,586,711 Patented June 22, 1971 ABSTRACT OF THE DISCLOSURE A series ofesters of acrylic and methacrylic acid containing in their alcoholresidue two or three ter-t-alkylamino or tert-amino groups of variousstructures. There are disclosed different methods for their production:by the reaction of dior triaminoalkanols with acrylic or methacrylicacids, their chlorides or lower alkyl esters.

This invention relates to novel esters of afi-llnstltllrated acids andto methods of manufacturing the same. More particularly, the inventionrelates to a method for the preparation of novel esters of acrylic andmethacrylic acids containing several amino groups in the alkoxylradical.

The compounds of this type are monomers whose molecule has easilypolymerizing double bonds and contains several secondary or tertiaryamino groups. When copolymerized with other vinyl monomers, smallquantities of acrylates or methacrylates containing only one amino groupin the alkoxyl radical are known to confer on the polymeric compoundsthus obtained good mechanical properties, high adhesion to diversematerials, improved dyeability, and better resistance to temperatureshocks. Highly basic anionites can be derived from such acrylates ormethacrylates.

It is apparent, that the monomers containing more than one amino groupwould exert a similar, but more pronounced effect. For example,ion-exchange resins derived from monomers that contain several aminogroups and, hence, have a high content of amino nitrogen would possess ahigher ion exchange capacity than ion-exchange resins prepared fromesters of unsaturated acids containing one amino group per monomericmolecule.

Heretofore, no esters of nap-unsaturated acids containing more than oneamino group in the alkoxy radical have been known.

It is an object of the present invention to provide esters ofa,,B-unsaturated acids that contain several secondary or tertiary aminogroups in the alkoxyl radical.

It is another object of the present invention to provide simple andeconomical methods of manufacturing the monomers of the above type whichlend themselves to commercial application.

These and other objects have been accomplished, according to the presentinvention, by reacting polyamino monohydric alcohols having the generalformula AOH with tip-unsaturated acids having the general formula RCHF-COOH or with chlorides of said unsaturated acids,

R CH )-OOCL or with lower alkyl esters of said unsaturated acids havingthe general formula Ill 0 oH,=C-( Jo R wherein R is hydrogen or a methylradical, R is an alkyl radical containing up to 4 carbon atoms, and Astands for R1 -C nHgnN-C nHEnN R1 C uHZn R1 C nHZnN wherein represents aradical selected from the series comprising secondary aliphatic,tertiary aliphatic and heterocyclic amino groups having from 2 to 12carbon atoms; R represents an alkyl radical having up to 6 carbon atoms,and n represents 2 or 3.

Acrylic and methacrylic acids as well as chlorides and lower alkylesters thereof required for the manufacture of monomers of the typespecified above are readily available commercial products. Polyaminomonohydric alcohols can be prepared from readily available commercialproducts. 1,3-bisaminoisopropanols are prepared by reaction appropriateamines with epichlorohydrin in accordance with the general reactionscheme set forth below:

In place of epichlorohydrin, use can be made of 0:,7- dichlorohydrin Nalkyl N (aminoalkyl) arninoalkanols are prepared by alkylatingappropriate alkylaminoalkanols with aminoalkyl halides in the presenceof alkaline agents according to the following reaction scheme:

alkaline agent wherein X stands for chlorine, bromine or iodine.

Esterification of a,B-unsaturated acids is carried out as follows. Intoa reaction vessel fitted with a stirrer, a thermometer, and a refluxcondenser with a water trap are charged an amino alcohol, acrylic ormethacrylic acid, a solvent for azeotropic distillation of the Waterformed, an esterification catalyst, and a polymerization inhibitor. Thereaction mixture is refluxed with stirring until aqueous layer ceases toseparate in the water trap, and thereafter cooled to room temperatureand treated with an alkaline agent to neutralize the unreactedunsaturated acid, next the solvent is distilled off and the residue isfractionated in vacuum. The reaction may be carried out at ambient,elevated or reduced pressure and in an atmosphere of air, nitrogen orsome other gas that is indifferent to the components of the reactionmixture. The temperature of the reaction mixture depends upon thesolvents and amino alcohol used, but it is usually maintained in the 80to 200 C. range. The esterification catalysts comprise sulfuric acid,ferric and aluminum sulfates, sodium bisulfate, and metallic sodium. Thepreferred esterification catalysts are ferric and aluminum sulfates inhydrated form taken in an amount of 0.1 to 10% by weight based on theweight of the reagents used.

Use is made of the following solvents: benzene, toluene, xylenes andother solvents capable of forming azeotropic mixtures with water. Thepolymerization inhibitors used include para-hydroxydiphenylamine,diphenyl-para-phenylenediamine, phenothiazine and other aromatic amines,as well as phenols and naphthols.

The monomeric polyamino esters of u,B-unsaturated acids are obtained bythe present method in a yield of 60-70% of the theoretical amount.

When recourse is had to chlorides of a e-unsaturated acids to acylateappropriate polyamino monohydric alcohols, the product compounds, viz.,monomeric polyaminoesters, are obtained in a yield better than 90% ofthe theoretical amount. The reaction is carried out as follows. To asolution of the chloride of an u,fl-unsaturated acid in an anhydroussolvent (benzene, toluene, diethyl ether, acetonitrile,dimethylformamide, etc.), maintained at a temperature of to 120 C.(preferably at 20 to 80 C.) and containing a polymerization inhibitor,is gradually added, with stirring, a solution of the stochiometricquantity of a polyamino monohydric alcohol in the same solvent. In orderto bring the reaction to completion, stirring the reaction mixture atelevated temperature is continued for a short period of time. Toliberate the free base of the monomeric polyaminoester from themonohydrochloride formed as a result of the reaction, the reactionproducts should be treated with an aqueous or alcoholic solution ofalkali or alkali earth metal carbonates or hydroxides. A solution of thefree base of the product ester in an organic solvent is separated froman aqueous solution of the metal salt (Where the reaction products havebeen treated with an aqueous solution of the alkaline agent) or freedfrom a metal chloride sediment by filtration (in case neutralization ofthe reaction products has been effected with an alcoholic solution), andthereafter fractionated.

In some instances it is expedient to carry out acylation in the presenceof compounds capable of combining the hydrogen chloride formed in thecourse of the reaction, pyridine, triethylamine and other tertiaryamines being suitable for this purpose. Acylation may likewise becarried out in the absence of a polymerization inhibitor which in thiscase should be added at the step of rectifying the product compound.

In accordace with the present invention, the most effective procedurefor the preparation of monomeric polyaminoesters of D li-unsaturatedacids comprises transesterification of lower alkyl esters of said acidswith corresponding polyaminoalcohols. The procedure involves heating amixture of a polyamino monohydric alcohol, a lower alkyl ester of ana,,8-unsaturated acid, taken preferably in excess, and a polymerizationinhibitor in a reaction vessel connected to a rectifying column, andadding to the reaction mixture a transesterification catalyst once themixture attains the desired temperaure. Where the starting reagentscontain some moisture, a small quantity of the alkyl ester of theunsaturated acid should be distilled off prior to adding thetransesterification catalyst to the reaction mixture so that the waterpresent in the reaction mixture will be removed in the form of anazeotrope with the starting ester. The required amount of the catalystis added all at once or in small portions throughout thetransesterification step. The lower alkanol formed is removed in theform of an azeotropic mixture with the starting alkyl ester. Thereaction is carried out at a temperature sufiiciently high for rapiddistillation of the azeotropic mixture. The temperature of theazeotropic mixture is usually maintained in the 60 to 160 C. range,preferably in the to 130 C. range. The reaction is carried out atambient, elevated or reduced pressure in an atmosphere of air, nitrogenor some other gas that is inert to the reaction mixture components. Whenthe lower alkanol has been distilled 0E in a nearly theoretical amount,the product polyaminomonoester of the a,,8-unsaturated acid is isolatedby distillation in vacuum or by other appropriate techniques.

The transesterification catalysts include alkali metals and alkoxidesthereof, as well as alkoxides of other metals, e.g. titanium andaluminum alkoxides, the most effective and convenient catalysts beingsodium methoxide in the form of a 25-30% solution in dry methanol andtitanium tetra-n-butoxide. It is expedient to employ said catalysts inan amount of 0.1-10 mol. percent, preferably in an amount of 1-5 mol.percent, based on the amino alcohol used.

The group of useful polymerization inhibitors comprises phenols,aromatic amines, and aminophenols, e.g., hydroquinone, 2,6di(tert.butyl) 4 methyl phenol (ionol), pyrocatechol,tert-alkylpyrocatechol, B,fi'-dihydroxy-a,a'-dinaphthyl (di-B-naphthol)phenyl-B-naphthylamine, N,N'-diphenyl-paraphenylenediamine,thiodiphenylamine (phenothiazine).

Transesterification under the conditions disclosed here'- inabove renderit possible to prepare monomeric polyamino esters of a-fl-unsaturatedacids in a yield of 80- of the theoretical amount based on the polyaminoalcohol introduced into the reaction mixture.

The present method was instrumental in synthesizing polyaminomonoestersof a,fl-unsaturated acids having the following structural formula:

i /O CH2=CC/ wherein R is a radical selected from the group consistingof hydrogen and methyl; A stands for a radical selected and R1 Hg N R1CnH nN is a ramcal selected from the series which consists of secondaryaliphatic, tertiary aliphatic and heterocyclic amino groups having from2 to 12 carbon atoms, e.g.,

R stands for an alkyl radical having up to 6 carbon atoms, and nrepresents 2 or 3.

The following novel compounds have been synthesized:

1,3-bis-(dimethylamino)-isopropyl methaerylate Hz CHCO O CI1[CHzN(0119212; 1,3-bis-(diethylamino)-isopropyl methacrylate UHF-1C (CH3) COOCHiCHzN (C2II5)2]z;

1,3-l)is-(diethylamino)-isopropyl acrylate GH =CH COO CH[OHzN(CzH)2]2;1,3-bis-(diallylamino)-isopropyl methyacrylate CH2=C (CH3) CO 0 CHlCHzN(CH2CH=CH2)2]2; 1,3-bis-(diallylamino) -isopropyl acrylate OH2=CHOOOCHICHQN (CHz-OH=CIT2)2]2;

1,3-di-(N-piperidyl)-isopr0pyl methaerylate1,3-dl-tert.butylaminoisoproyl methacrylate CH2=C (CH3) COO CH[CH2NHC(CH3) 1,3-(li-tert.hexylaminolsopropyl rnethacrylate CH2=C (CH3) COOCH[CHNHG(CH3)2C H2CH2CI'I312} Ldiethylamino-S-dlallylamlno-isopropylacrylate CH2 C2H5) 2 CHFCH 000 CH 2 (CHzCH=CH gl-diethylamino-3-(N-piperidyl) isopropyl acrylate CH OHrCfig1-diat]rylamino-3-(N-piperldyl)-isopropyl mothacrylate CHz-CHg CH CH2-C2l-diethylzmrino-B-(N-morplrolyD-isopropyl methaorylate CH -CH CH GHCOOCH CH2=O(CH3)OOOCH CHFC (CHa)OOOCH CH -N CHz-Gfig 2[N'methyl-N-(Z-dimethylaminoethyl) -amlno]'ethyl methacrylateUHF-(X0113) CO0 GHzCH I I-CH OH N(CH3)Z-[N-methyl-N-(Z-dimethylaminoethyl)-amino]-ethyl acrylate CH3 CH =CHC 0O CHZCH2I ICHZCHZN(CH3)Q2-[N-methyl-N-(Z-diethylaminoethyl)-amino1-ethyl acrylate CHa CH =CHC OO CHzCHzI ICH CHzN(CgH5)z2-[N-allyl-N-(2-diethylaminoethyl)-amino]-ethyl ncrylate CH2- 0 H: C H3CH2==OHC O 0 CH2CH2N CHzCH2 (C2 5); 2-lN, N bis- (2-diethylamiuoethyl)-an1in01-etl1y1 acrylate OH; CHZN(CZH5)Z CHFCHCO O CHZCEDH CH2CH3N(0211502 3-[N,N-bis-(2-dirnethylaminoethyl) amino]-propyl methacrylate CH-CHgN(CHa)2 CHg=C(CHa) C O O CH2CH2CH N CH2 CHzN(CH3)2 3-[N,N-bis-(Z-diethylaminoethyD-arninol-propyl methaerylate 2CH2 (C2 s)2CH2=O (CH3) 0 O O CHzCHzCHz CH -CH2N(C H Acrylic and methacrylic estersof and esters polyamino monohydric alcohols prepared according to thepresent invention are colorless liquids which are soluble in organicsolvents.

Esters, which contain dimethylamino groups, are readily soluble inWater, whilst the solubility of other esters in water diminishesmarkedly with the increasing chain length of substituents at nitrogenatoms in the amino groups. When mixed with methyl iodide, amino esterscontaining tertiary amino groups yield appropriate quaternary salts. Toobtain hydrochlorides of amino esters, dry hydrogen chloride should bebubbled through amino esters dissolved in organic solvents.

Hydrochlorides and alkoiodidesof the esters of the present invention arecolorless crystals which are readily soluble in water. Picrates can becrystallized from alcoholic solutions in the form of yellow crystals.

In the presence of azo-diisobutyrodinitrile and at an elevatedtemperature (40 to C.), the monomeric polyamino esters undergo rapidpolymerization yielding colorless, transparent polymers which vary inhardness from a soft resin to a hard, glassy resin. Polymerization ofthe obtained monomeric esters, in the course of storage, is prevented byadding small amount (0.05 to 0.5% by weight) of the same polymerizationinhibitors as those used in the process of manufacturing said esters.

The present invention makes it possible to obtain in high yields theesters of a,B-Un8al2lll'8t6d acids and polyamino monohydric alcohols bya method which can be readily adapted on an industrial scale.

For a better understanding of the present invention, the followingexamples are presented by way of illustration.

EXAMPLE 1 1,3-bis- (dimethylamino -isopropyl-methacrylate CHQN CH3 2 OH=(lJCOCE OH; CH2N(CH3)Z Into a flask connected to a fractionating columnhaving an efficiency of ca. 10 perfect plates are charged 72 g. of1,3-bis-(dimethylamin0)-isopropanol, 150 g. of technical methylmethacrylate, and 1.5 g. of para-hydroxy-diphenylamine. The reactionmixture is heated to 90 C. on an oil bath, and then to it is added 0.5ml. of a 25% solution of sodium methoxide in dry methanol. The catalystis further added to the reaction mixture every -10 minutes in an amountof 0.1 to 0.2 ml. until the total amount of the catalyst added reaches 3to 4 ml. The temperature of the oil bath is maintained at 120 to 140 C.throughout the entire reaction period.

The methanol formed in the course of the reaction is distilled off as anazeotrope with methyl methacrylate at a vapor temperature of 6466 C. Thecontent of methanol in the mixture is estimated by the refractometrictechnique. A nearly theoretical amount of methanol is formed in thecourse of 2.5 to 3 hours. Next the reaction mixture is cooled to roomtemperature; filtered from traces of a precipitate and fractionatedthrough a short column under reduced pressure. Upon separation of theunreacted methyl methacrylate, the material that distils at 117117.5C./20 mm. consists of pure 1,3-bis-(dimethylamino)-isopropylmethacrylate.

The yield is 95.7 g. (89.4% of the theoretical amount); n 1.4475; d0.9239; MR 62.00; MR 62.06.

Analysis.Found (percent): N, 12.98; 12.87. Calcd. for C H N O (percent):N, 13.07.

To identify the esters obtained, it is reacted with methyl iodide.

Dimethiodide colorless crystals (from ethanol); M.P. 218219 C. (withdecomp.).

Analysis.Found (percent): N, 5.63; 5.73. Calcd. for C13H23I2N202(percent): N, 5.62-

EXAMPLE 2 1,3-bis- (dimethylamino -isopropyl acrylate CHgN CH3) 2CH2=CHC O OCH 0 H N C Ha) 2 Into a 4-necked flask fitted with amechanical stirrer, a thermometer, a dropping funnel, and a refluxcondenser with calcium chloride tubes are placed 18.2 g. of acryloylchloride, 0.5 g. of para-hydroxydiphenylamine, and 100 m1. of drybenzene. A solution of 29.2 g. of 1,3-bis-(dimethylamino)-isopropanol in20 ml. of dry pyridine is added Within 30 minutes, with stirring, to thereaction mixture maintained at 25-30 C. The mitxure is heated to 80 C.and stirred for an additional hour, followed by cooling the mixture toroom temperature and adding, also with stirring, a solution of 11.5 g.of potassium hydroxide in 40 ml. of methanol. The precipitate that formsis removed by filtration and the filtrate is distilled in vacuum toyield 30.1 g. of 1,3-bis-(dimethylamino)-isopropyl acrylate (75.3% ofthe therotical amount); B.P. 99-100/18 mm.; 11, 1.4478; r1 0.9290; MR57.69; MR 57.45.

Analysis.-Found (percent): N, 13.70; 13.87. Calcd. for CmHggNzOz(percent): N, 13.98.

Dimethiodide: M.P. ZOO-201 C. (from ethanol).

Analysis.Found (percent): N, 5.57. Calcd. for C H I N O (percent): N,5.78.

EXAMPLE 3 1,3-bis- (dimethylamino -isopropyl methacrylate CHZN(CZH5) zCHz=C (CHa)C O O CH CH2N (02135):

(a) Into the transesterification reaction vessel described in Example 1are placed 101 g. of 1,3-bis-(diethylamino)- isopropanol, 1.5 g. ofpara-hydroxydiphenylamine, and 150 g. of methyl methacrylate. Thereaction mixture is heated to 90 C. and to it is added 1 ml. of asolution of sodium methoxide in dry methanol, followed by adding thecatalyst in 0.2-m1. portions every 10 min. The total amount of thecatalyst solution incorporated during 2 hours equals 3.2 ml., and 24.4of an azeotropic mixture containing 17.8 g. of methanol is distilledduring the same period. After filtering and distilling in vacuum thereaction products, 1,3-bis-(diethylamino)-isopropyl meth acrylate isobtained in a yield of 115.2 g. (85.4% of the theoretical amount; B.P.118-120 C./6 mm.; 11 1.4528; dfi" 0.9104; MR 80.26; MR 80.53.

Analysis.-Found (percent): N, 10.30; 10.48. Calcd. for C H N O(percent): N, 10.37.

(b) Into a round-bottomed flask fitted with a stirrer, a thermometer,and a reflux condenser with a water trap, are charged 60.5 g. of1,3-bis-(dimethylamino)-isopropanol, ml. of m-xylene, 2 g. ofdiphenyl-para-phenylenediamine, 3 g. of ferric sulfate, Fe (SO '9H O,and 28.4 g. of methacrylic acid. The temperature of the reaction mixturerises spontaneously to 50 C. The mixture is then boiled with stirring at150-170 C. for 3 hours, and 5.3 ml. of an aqueous phase containing asmall amount of methacrylic acid collects during this period in thetrap. Next the reaction mixture is cooled to room temperature, Washedwith an aqueous solution of potassium carbonate and fractionated througha short column under reduced pressure. Upon removal of m-xylene, theredistils the unchanged 1,3-bis-(diethylamino)-isopropanol (11.5 g., B.P.8487 C./ 3 mm.; n 1.4770), next distils a small intermediate fraction(2.5 g.; B.P. 87108 C./3 mm.; 11. 1.4498), and finally collects pure1,3-bis-(diethylamino)-isopropyl methacrylate (B.P. 108-112" C./ 3 mm.;11 1.4528). The diamino ester is obtained in a yield of 57.1 g. (70.4%based on the diamino alcohol charged or 92.3% based on the converteddiamino alcohol).

EXAMPLE 4 1, 3-bis- (diethylamino -isopropyl acrylate 0 CH=CH-C CH2NC2115) 2 O CH CH2N( zHs) 2 (a) Into the reaction vessel described inExample 2 are charged ml. of dry benzene, 10 g. of acryloyl chloride,and 1 g. of para-hydroxydiphenylamine. Then to the mixture is added,with striring, during 3040 minutes a solution of 20.2 g. of1,3-bis-(diethylamino)-isopropanol in 30 ml. of benzene, the temperatureof the reaction mixture being maintained below 50 C. In 15 minutes afteradding all the diamino alcohol, 11 g. of triethylamine is incorporatedinto the reaction mixture, which is stirred additionally for 30 minutes,and cooled thereafter to room temperature. Then to it is added asolution of 6 g. of potassium hydroxide in 30 ml. water. This results inreaction mixture layering. The organic layer is washed twice with water.Next the solvents are removed by distillation, and the residue isfractionated in vacuum. The yield of 1,3-bis-(diethylamino)-isopropylacrylate is 23.8 g. (93.1% of the theoretical amount); B.P. 8788 C./1mm.; 12 1.4510; d 0.9124. MR 75.71; MR 75.92.

Analysis.Found (percent): N, 10.88; 10.90. Calcd. for C H N O (percent):N, 10.93.

Dimethiodide: M.P. 185-186 C. (from ethanol).

Anulysz's.--Found (percent): N, 5.09; 5.23. Calcd. for C H I N O(percent): N, 5.19.

(b) Into a round-bottomed flask fitted with a thermometer, a refluxcondenser with a water trap, and a tube that reaches nearly to the flaskbottom and serves for gas delivery, are placed 101 g. of1,3-bis-(diethylamino)-isopropanol, 50 g. of m-xylene, 3 g. of hydratedaluminum sulfate, Al (SO -18H O, 4 g. of diphenyl-para-phenylenediamine,and 36 g. of acrylic acid. The temperature of the reaction mixture risesto 55 C. Dry nitrogen is then bubbled through the reaction mixture whichis boiled on an oil bath. The water that forms in the course of thereaction and contains an admixture of acrylic acid is collected in thetrap, from which it is periodically removed. The total amount of theaqueous phase that distils at a temperature of 140155 C. during 5 hoursis 15.6 ml. Next the reaction mixture is cooled to room temperature andtreated, while continuing to purge the mixture with nitrogen, with a 40%aqueous solution of sodium hydroxide, followed by washing the organiclayer with a sodium chloride solution, drying it over anhydrousmagnesium sulfate, and distilling through a short column. Distillationyields 10.2 g. of unreacted diamino alcohol, a small intermediatefraction, and 77.45 g. of 1,3-bis-(diethylamino)-isopropyl acrylate(60.5% of the theoretical amount); B.P. 86--89 C./1 mm.; n 1.4513. Thediamino ester is obtained in a yield of 75.7% based on the converteddiamino alcohol.

EXAMPLE 5 1,3-bis-(diallylamino)-isopropyl methacrylate 25.0 g. of1,3-bis-(diallylamino)-isopropanol and 30 g. of methyl methacrylate inthe presence of 1 g. of di-,B- naphthol and sodium methoxide yield,under the conditions disclosed in Example 1, 30.1 g. of1,3-bis-(diallylamino)-isopropyl methacrylate (94.7% of the theoreticalamount); B.P. 136-138" C./2 mm.; n 1.4778; d 0.9278. MR 97.06; MR 97.14.

Analysis.-Found (percent): N, 8.76; 9.02. Calcd. for C H N O (percent):N, 8.79

To a solution of 10 g. of acryloyl chloride in 100 ml. of dry benzene,placed in a reactor described in Example 2, is added with stirring, fora period of 40 minutes a solution of 25 g. of1,3-bis-(diallylamino)-isopropanol in 30 m1. of benzene, the temperatureof the reaction mixture being kept at about 50 C. Next the reactionmixture is heated to a temperature of 75-80 C. and stirred for anadditional hour; it is then cooled to room temperature and treated with100 g. of a 10% aqueous solution of potassium hydroxide. The organiclayer that separates is washed with water; after the addition of 0.5 g.of di-flnaphthol, benzene is removed by distillation, and the 110residue is fractionated in vacuum. l,3-bis-(diallylamino)- isopropylacrylate is obtained in a yield of 27.1 g. (89.1% of the theoreticalamount); B.P. 135137 C./2.5 mm.; n 1.4788; d 0.9390. MR 91.90; MR 92.52.

Analysis.--Found (percent): N, 9.25; 9.28. Calcd. for C H N O (percent):N, 9.21.

EXAMPLE 7 1,3-di- (N-piperidyl -isopropy1 methacrylate The reaction iscarried out by following the procedure disclosed in Example 1. From 67.8g. of 1,3-di-(N-piperidyl)-isopropanol and g. of methyl methacrylate isobtained 75.5 g. of 1,3-di-(N-piperidyl)-isopropyl methacrylate (85.6%of the theoretical amount). The reaction comes to completion within 3 to3.5 hours. The product boils at 132133 C./1 mm.; 11 1.4844; (1 0.9808.

Analysis.Found (percent): N, 9.27; 9.41. Calcd. for MR 85.86; MR 85.37.

C H N O (percent): N, 9.51.

EXAMPLE 8 1,3-di-(N-piperidyl)-isopropyl acrylate GE -CH CH GHQ-CZ GH-CH CH2 CHrCE Ig C H N EXAMPLE 9 1,3-di-(tert.butylamino)-isopropylmethacrylate CH =C(CH )-COOCH [CH NHC(CH 1 In the same manner asdisclosed in Example 1, 72.1 g. of 1,3-di-(tert.butylamino)-isopropanolis reacted with g. of methyl methacrylate in the presence of 2 g. ofdi-B-naphthol and sodium methoxide to give 71.2 g. of1,3-di-(tertbutylamino)-isopropyl methacrylate (74.5% of the theoreticalamount); B.P. 104108 C./1 mm.; 11 1.4470.

Analysis.Found (percent): N, 10.08; 10.15. Calcd. for C H N O (percent)N, 10.37. Neutralization equiv alent found, 135.5; neutralizationequivalent calcd., 135.

Dipicrate: yellow crystals (from methanol), M.P. 205- 206 C.

1 1 EXAMPLE 10 1,3-di-(tert.hexylamino)-isopropyl methacrylate CH3 H1-diethylamino-3-diallylamino-isopropyl acrylate o CH2=CHO CH2N(C2H5)2OCH CH2N(CHzCI =CH2)z In the same manner as disclosed in Example 6, 9 g.of acryloyl chloride and 18.1 g. of1-diethylamino-3-diallylaminoisopropanol give 20.5 g. of1-diethylamino-3-diallylamino-isopropyl acrylate (91.5% of thetheoretical amount); B.P. 91.5 C./0.4 mm.; n 1.4622; 11 0.9249. MR84.00; MR for C H N O (percent): N, 9.99.

EXAMPLE l2 1-diethylamin0-3-(N-piperidyl)-isopropyl acrylate CHz (C2 20112 GH -CH3 In the same manner as disclosed in Example 6, 21.4 g. of1-diethylamino-3-(N-piperidyl)-isopropanol and 9.9 g. of acryloylchloride yield 25.3 g. of 1-diethylamino-3-(N- piperidyl)-isopropylacrylate (84.4% of the theoretical amount); B.P. 9394 C./0.4 mm.; n1.4693; (Z 0.9553. MR 78.29; MR 78.34.

Analysis.Found (percent): N, 10.03. Calcd. for C15H28N202 (percent): N,10.42.

EXAMPLE 13 1-diethy1amino-3- (N-piperidyl) -isopropyl methacrylate Inthe same manner as disclosed in Example 6, 7.8 g. of acryloyl chlorideand 15.77 g. of 1-diethylamino-3-(N- piperidyl)isopropanol give 18.2 g.of 1-diethylamino-3- (N-piperidyl)isopropyl methacrylate (88.5% of thetheoretical amount); B.P. 98-100 C./05 mm.; n 1.4684; 01 0.9431. MR83.28; MR 83.155.

Analysis.Found (percent): N, 10.15; 10.30. Calcd. for C H N O (percent):N, 9.94.

1 2 EXAMPLE 14 1-diethylamino-3- (N-rnorpholyl -isopropyl methacrylate(3H3 O CHFC- C CHz (C2 s) 2 0 -CH GH CH CH N CH -CH,

In the transesterification reaction vessel described in Example 1, areplaced 24.4 g. of 1-diethylamino-3-(N- morpholyl)isopropanol, 34 g.methyl methacrylate, 1 g. of diphenyl-paraphenylenediamine, and 0.5 ml.of a 25% solution of sodium methoxide in dry methanol. The reactionmixture is heated on an oil bath so that the azeotropic mixture ofmethanol and methyl methacrylate distils at a vapor temperature of 6465C. Next 0.3 ml. of the catalyst solution is added to the reactionmixture in 0.1 ml. portions every 15-20 minutes. The reaction iscompleted within 1 hour. The mixture is filtered and distilled invacuum. The yield of 1-diethylamino-3-(N- morpholyl)isopropanolmethacrylate is 24.4 g. (75.5% of the theoretical amount); B.P. 116 C./0.7 mm.; 11 1.4690.

Analysis.-Found (percent): N, 9.50; 9.74. Calcd. for C15H28N203(pfircellt): N,

EXAMPLE 15 2- [N-methyl-N- Z-dimethylaminoethyl -amino] ethylmethacrylate In the same manner as dislcosed in Example 1, 72 g. of 2 [Nmethyl N-(Z-dimethylaminoethyl)-amino]- ethanol and g. of methylmethacrylate give 96.6 g. of the corresponding diamino ester (90.2% ofthe theoretical amount); B.P. 96.5 C./4 mm.; n 1.4557; d 0.9405. MR61.90; MR 62.06.

Analysis.Found (percent): N, 12.88; 12.99. Calcd. for C H N O (percent):N, 13.07.

EXAMPLE l6 2- [N-methyl-N- Z-dimethylaminoethyl) -amino] ethyl acrylateIn the transesterification reaction vessel described in Example 1 areplaced 72 g. of 2-[N-methyl-N-(2-dimethylaminoethyl)-amino]-ethanol, 129g. of methyl acrylate, 1 g. of para-hydroxydiphenylamine and 5 g. oftitanium tetra-n-butoxide. The reaction mixture is heated withconcomitant distillation of the azeotropic mixture of the methanolformed and methyl acrylate at a vapor temperature of 62.564 C. Theamount of methanol collected equals 14.6 g. (91% of the theory). Excessmethyl acrylate is distilled under reduced pressure produced by awater-jet pump, and the residue is distilled in vacuum through a shortrectifying column to yield 85.7 g. of 2-[N-methyl-N-(2-dimethylaminoethyl)-amino]-ethyl acrylate (85.7% of thetheoretical amount); B.P. 8992 C./6 mm.; 11 1.4552; d 0.9495. MR 57.25;MR 57.45.

Analysis.Found (percent): N, 13.73; 13.82. Calcd. for C H N O (percent):N, 13.95.

Dimethiodide: M.P. 176179 C. (With decomp.).

Analysis.-Found (percent): I, 52.40; N, 5.32. Calcd. for C12H26I2N202(percent): 1, N, 5.78-

1 3 EXAMPLE 17 2- [N-methyl-N- (2-dimethylaminoethyl -arnino ethylacrylate In the same manner as disclosed in Example 16, 17.4 g. of 2-[N-methyl-N- (Z-diethylaminoethyl) -amino] -ethanol and 25.8 g. ofmethyl acrylate yield 18.4 g. of the corresponding diamino ester (80.7%of the theoretical amount); B.P. 109-110 C./6 mm.; n 1.4540; d 0.9257.MR 66.80; MR 66.68.

Analysis.-Found (percent): N, 12.16; 12.32. Calcd. for C H N O(percent): N, 12.27.

EXAMPLE 18 2- N-allyl-N- (2-diethylaminoethyl) -amino] ethyl acrylateInto the transesterification reaction vessel are placed 20.0 g. of2-[N-allyl-N-(Z-diethylaminoethyl)-amino]- ethanol, 34.4 g. of methylacrylate and 1 g. of diphenylpara-phenylenediamine. The reaction mixtureis brought to boiling and a few grams of methyl acrylate are allowed todistil in order to remove the traces of moisture that might be presentin the mixture; then 1 g. of titanium tetraisopropoxide is added to thereaction mixture and, within several minutes, the vapor temperaturedrops to the boiling point of the azeotropic mixture of methanol andmethyl acrylate. Within 65 minutes, there distils 7.1 g. of theazeotropic mixture containing 2.92 g. of methanol, so that thetransesterification is 93.3% complete. The reaction products aredistilled in vacuum to yield 19.3 g. of the corresponding diamino ester(75.8% of the theoretical amount): B.P. 107109 C./2 mm.; n 0.9338. MR75.14; MR 75.45.

Analysis.Found (percent): C H N O (percent): N, 12.88.

EXAMPLE '19 2- N,N-bis- Z-diethylaminoethyl) amino] -ethyl acrylate N,12.66. Calcd. for

To a solution of g. of acryloyl chloride in 50 ml. of dry acetonitrileis added within 20 minutes, with stirring, a solution of 25.9 g. of2-[N,N-bis-(2-diethylaminoethyl)- amino]-ethanol in ml. of acetonitrile,the temperature of the mixture being maintained below 50 C. The mixtureis boiled for an additional hour, cooled to room temperature, and to itis added 4.5 g. of dry powdered sodium hydroxide, the mixture beingstirred until the powder dissolves completely. Sodium chloride thatprecipitates is removed by filtration, to the filtrate is added 0.1 g.of phenothiazine, the solvent is distilled off, and fractionation of theresidue in vacuum yields 23.6 g. of the corresponding triamino ester(75.4% of the theoretical amount); B.P. 145-149 C./0.80.9 mm.; n 1.4650.

Analysis.Found (percent): N, 13.67; 13.71. Calcd. for C I-1 N 0(percent): N, 13.41.

1 4 EXAMPLE 20 3-[N,N-bis-(Z-dimethylaxminoethyl)-amin0] -propylmethacrylate Into the transesterification reaction vessel are placed21.7 g. of 3-[N,N bis (Z-dimethylaminoethyl)-amino]- propanol, 30 g. ofmethyl methacrylate, 0.3 g. of phenothiazine, and 1 g. of titaniumtetra-n-butoxide. The reaction mixture is heated and the azeotropicmixture of methanol and methyl methacrylate distils at 64-65 C. so that2.88 g. of the theory) of methanol collects during 45 minutes. Vacuumdistillation of the reaction products gives 22.9 g. of3-[N,N-bis-(Z-dimethylaminoethyl)-amino]-propyl methacrylate in the formof a colorless liquid; B.P. 9093 C./1 mm.; n 1.4576.

Analysis.Found (percent): N, 14.46; 14.37. Calcd. for C H N O (percent):N, 14.72.

EXAMPLE 2 l 3- N,N-bis- 2-diethylaminoethyl -amino] -propyl methacrylatel OH2=CC cmoH NwzHm In the same manner as disclosed in Example 20, 13.7g. of 3-[N,N-bis-(Z-diethylaminoethyl)-amino]-propanol and 20 g. ofmethyl methacrylate in the presence of 1 g. of titanium tetra-n-butoxideand 0.2 g. of phenothiazine give 12.6 g. of the corresponding trialminoester (74.2% of the theoretical amount); B.P. 130-134 C./0.5 mm.; 111.4680; d 0.9190. MR 103.3; MR 102.95.

Analysis.-Found (percent): N, 12.41; 12.48. Calcd. for C H N O(percent): N, 12.30.

EXAMPLE 22 3- N,N-bis- 2-diethylaminoethyl) -amino] -propyl acrylateCHFCH-C O CHgCHgCHgN To a solution of 5 g. of acryloyl chloride in 30ml. of anhydrous dimethylformamide placed in the reaction vesseldescribed in Example 2, is added, with stirring, in the course of 20minutes a solution of 13.65 g. of 3-[N,N-bis-(Z-diethylaminoethyl)-amino]-propanol in an equal volume of dimethylformamide. The temperature of the reaction mixture rises from roomtemperature to 50 C. The reaction mixture is then heated to C. andstirred for an additional 30 minutes, followed by cooling and adding toit a solution of 3 g. of sodium hydroxide in 4 ml. water. The sodiumchloride that precipitates is filtered off, and the filtrate isfractionated in vacuum to yield 12.55 g. of3-[N,Nbis-'(2-diethylaminoetl1yl)- amino] propyl acrylate (76.8% of thetheoretical amount); B.P. l39142 C./0.6 mm.; 11 1.4670; df 0.9292. MR97.81; MR 98.33.

15 16 Analysis-Found (percent): N, 12.82; 12.85. Calcd. or for"C13H37N302 (pfircent): N, 12-83. CH CHzNR Rg We claim: (OH2 DN 1. Anester having the formula:

5 OH2CH2NR1R2 l (I) -NR1R2 is tert-C H NH, teIt-C H13NH, CHFCC-O-A .(CHwherein R is hydrogen or methyl; A is 10 gfigfig S N R3 ls methyl orCHZNRIRZ No references cited. O\ ALEX MAZEL, Primary Examiner CHZNRIRI15 J. TOVAR, Assistant Examiner R3 US. Cl. X.R.

1 -(CH2 1NH1CH2NR1R1 260-2.1, 89.5, 247.2, 294.3.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Inventor(s)Mikhail Alexeevich Korshunov et a1 Patent No.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 16, line 7: change "(CH2)2N to --(CH3)2N-,--

line 8: change "(C3H5)2N-" to --(C2H5)2N- Signed and sealed this 6th dayof August 1971+.

(SEAL) Attest:

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner ofPatents

